CN114361581A - Calcium metal battery electrolyte and calcium metal battery based on same - Google Patents

Calcium metal battery electrolyte and calcium metal battery based on same Download PDF

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CN114361581A
CN114361581A CN202210005889.7A CN202210005889A CN114361581A CN 114361581 A CN114361581 A CN 114361581A CN 202210005889 A CN202210005889 A CN 202210005889A CN 114361581 A CN114361581 A CN 114361581A
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calcium
calcium metal
electrolyte
metal
metal battery
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CN114361581B (en
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曹瑞国
韩叶虎
焦淑红
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University of Science and Technology of China USTC
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0563—Liquid materials, e.g. for Li-SOCl2 cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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Abstract

The invention discloses a calcium metal battery electrolyte and a calcium metal battery based on the same. The electrolyte additive can regulate and control the electrodeposition behavior of calcium metal and improve the interfacial reaction kinetics and surface SEI stability of calcium metal electrodeposition/stripping, thereby effectively avoiding the dendritic growth of calcium metal and the further passivation of the electrolyte on the calcium metal and realizing the stable and long circulation of high coulomb efficiency of a calcium metal battery.

Description

Calcium metal battery electrolyte and calcium metal battery based on same
Technical Field
The invention belongs to the technical field of calcium metal batteries, and particularly relates to a calcium metal battery electrolyte and a calcium metal battery based on the same.
Background
As an important energy storage and conversion device, a lithium ion battery plays an important role in national economy and modern life, but due to the limited energy density of the lithium ion battery and the scarce lithium resource storage capacity of the earth, the lithium ion battery cannot meet the increasing demands of people. Therefore, development of a new battery system is urgently required.
Among them, calcium metal batteries using metal calcium as a negative electrode and a calcium storage material as a positive electrode have attracted much attention in recent years due to their high energy density and extremely large calcium storage capacity. Compared with the lithium ion battery, the calcium metal cathode has higher theoretical specific capacity (1337mAh g)-1、2073mAh mL-1) And a lower electrochemical potential (-2.868V vs. she), making calcium metal batteries promising further improvements in the energy density of secondary batteries. And the reserves of calcium are abundant, and the reserves in the crusta are ranked fifth and are more than 1000 times of that of lithium. Therefore, it is possible to replace lithium ion batteries with calcium metal batteries. However, calcium metal and electrolyte have side reactions, and a passivation layer which is difficult for divalent calcium ions to pass through is formed on the surface of calcium metal, so that the process of electrodepositing calcium cannot be realized or the overpotential is large, and the research of calcium metal batteries is in a slow development state. In documents (y.jie, y.tan, l.li, y.han, s.xu, z.zhao, r.cao, x.ren, f.huang, z.lei, g.tao, g.zhang, s.jiao, angelw.chem., int.ed.engl.2020,59,12689), a calcium borohydride and lithium borohydride double-salt electrolyte system is reported, and the desolvation energy of calcium ions is reduced by the participation of lithium ions in coordination, thereby realizing advanced performance of 200 times of reversible electrodeposition of calcium metal and having an average coulombic efficiency of 97.6%. However, there are still insufficient cycle life, insufficient coulombic efficiency, use of noble metal Au as current collector and presence of CaCO3Etc. are disadvantageous for Ca2+Interface layers for transmission, and the like. It has also been shown that calcium metal often grows as dendrites which not only easily lose electrical contact with the substrate causing loss of active calcium, but can even penetrate the membrane causing a short circuit. It can be seen that the electrodeposition behavior and the interface composition of calcium metal play a crucial role in the performance of calcium metal batteries.
The electrolyte additive is one of effective methods for regulating and controlling metal electrodeposition behaviors and electrode interfaces, so that the development of the effective electrolyte additive for improving the calcium metal electrodeposition behaviors and the negative electrode interface components is an important strategy for improving the coulombic efficiency and prolonging the service life of the calcium metal battery. In addition, finding an inexpensive current collector compatible with the calcium metal battery to replace the existing platinum and precious metal current collectors is one of the important directions for promoting the practical development of the calcium metal battery.
Disclosure of Invention
In order to solve the problems of dendritic growth of calcium metal and poor interface dynamics of a calcium metal cathode commonly existing in a calcium metal battery, the invention aims to provide a calcium metal battery electrolyte and a calcium metal battery based on the calcium metal battery electrolyte, wherein a proper electrolyte additive is selected to regulate and control the calcium metal electrodeposition behavior, and a stable solid electrolyte interface phase (SEI) through which calcium ions can easily pass is constructed on the surface of an electrode to inhibit the dendritic growth and surface passivation of the calcium metal commonly existing in the calcium metal electrodeposition process, so that the high coulomb efficiency stable long cycle of the calcium metal battery is realized. Meanwhile, in order to solve the problem of using noble metal gold and platinum as the current collector of the negative electrode, the invention also provides a low-cost current collector of the negative electrode, so that the current collector has the battery performance equivalent to that of the noble metal gold and platinum as the current collector of the calcium metal battery, and meanwhile, the provided current collector has good compatibility with calcium metal and electrolyte in the calcium metal battery.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention firstly provides a calcium metal battery electrolyte, which is characterized in that: comprises a solvent, a calcium salt and an additive, wherein the additive is at least one of sodium borohydride and potassium borohydride. Sodium or potassium ions in the electrolyte can be deposited in the form of metallic sodium or potassium before calcium ions, and then calcium metal nucleates and grows by taking the metallic sodium or potassium as nucleation sites to form tightly-packed spherical calcium metal. The calcium metal balls tightly packed not only avoid the formation of calcium dendrites, but also are not easy to be separated from the substrate, and simultaneously, the contact area of the electrolyte and the calcium metal is reduced, and the side reaction is reduced. In addition, a sodium/calcium or potassium/calcium mixed SEI layer can be formed on the surface of the calcium metal, and the SEI layer is favorable for the transmission of calcium ions.
Further, the solvent is at least one of tetrahydrofuran, dimethyltetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, 1, 3-dioxolane, dimethyl sulfoxide, ethylenediamine, N-dimethylformamide and pyridine.
Further, the calcium salt is one or more of calcium bis (tetrahydrofuran) borohydride, calcium tetrafluoroborate, calcium hexafluorophosphate and calcium trifluoromethanesulfonate.
Further, in the electrolyte, the concentration of the calcium salt is 0.5-2.0 mol/L, and the concentration of the additive is 0.01-0.5 mol/L.
The invention also provides a calcium metal battery, which comprises a calcium metal negative electrode, a negative current collector, electrolyte, a positive electrode and a diaphragm. The electrolyte is added with sodium borohydride and/or potassium borohydride additives.
Further, the negative current collector adopts a carbon-coated aluminum foil, a carbon-coated copper foil or other carbon material substrates. The carbon-coated substrate or the carbon material substrate is beneficial to the preferential deposition of sodium or potassium ions in the electrolyte as sodium or potassium metal, and the sodium or potassium metal further induces the deposition of calcium metal.
Further, at least one of sodium metal and potassium metal is supported on the negative electrode current collector. The current collector loaded with sodium or potassium metal can induce calcium metal deposition in an unlimited manner including, but not limited to, direct roll loading or electrodeposition.
Further, at least one of sodium borohydride and potassium borohydride is loaded on the diaphragm. The sodium borohydride or the potassium borohydride loaded on the diaphragm can be dissolved in the electrolyte, which is equivalent to adding the sodium borohydride or the potassium borohydride in the electrolyte. The loading manner is not limited, and includes, but is not limited to, coating the additive on the electrode or the separator after coating the additive in the organic polymer.
Based on the above, the present invention further provides a method for improving the performance of a calcium metal battery, which comprises at least one of three ways: adding at least one of sodium borohydride and potassium borohydride as an additive into the electrolyte; loading at least one of sodium metal and potassium metal on a negative electrode current collector; at least one of sodium borohydride and potassium borohydride is loaded on the membrane.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the invention, sodium borohydride and/or potassium borohydride are/is added into the electrolyte of the calcium metal battery as an additive, so that the deposition of calcium metal in a spherical shape can be regulated and controlled, and the problems of active calcium loss and safety caused by dendritic growth of calcium metal are avoided. In addition, the electrolyte additive can also form a stable SEI layer through which calcium ions can easily pass on the surface of the calcium metal electrode, so that the calcium ions can be ensured to pass through, and the electrolyte can be effectively prevented from further corroding and passivating the calcium metal. The electrolyte additive can obviously inhibit the dendritic growth of calcium metal and improve the problem of poor dynamics of a calcium metal negative electrode interface, and realizes that the average coulombic efficiency of a calcium metal half-cell is kept more than 99.2 percent and stably circulated for more than 1000 times, which is far beyond the highest level of the world at present.
2. The electrolyte additive is an industrialized product, has low price, convenient use and very small using amount, and only accounts for 0.04-2 wt% of the total mass of the electrolyte.
3. The calcium metal battery negative current collector adopts a carbon-coated aluminum foil, a carbon-coated copper foil or other carbon material substrates, and has the following advantages: the compatibility with electrolyte, calcium metal and other materials in the battery is good; the weight is light, and the energy density of the battery is favorably improved; the price is low, and the cost of the calcium metal battery is greatly reduced.
4. The electrolyte additive and the current collector provided by the invention have milestone significance for promoting the development of the calcium metal battery.
Drawings
FIG. 1 shows the calcium metal half-cell at 1mA cm for comparative example 1 and example 1-2Deposition of 0.5mAh cm at current density of-2Long cycle performance comparison of deposition capacity of (a).
FIG. 2 shows the calcium metal half-cell at 1mA cm for comparative example 1 and example 1-2Deposition of 0.5mAh cm at current density of-2First loop deposition/lift-off curve of deposition capacity.
Fig. 3 is a cyclic voltammogram of the calcium metal half-cells of comparative example 1 and example 1.
Fig. 4 is a tafel plot for the calcium metal half-cells of comparative example 1 and example 1.
Fig. 5 is an electrochemical impedance spectrum of the calcium metal half-cell of comparative example 1 and example 1.
FIG. 6 shows the calcium metal half-cell of comparative example 1 at 1mA cm-2Deposition of 0.5mAh cm at current density of-2SEM topography of the deposition product on the working electrode after the deposition capacity of (1).
FIG. 7 shows a calcium metal half-cell of example 11mA cm-2Deposition of 0.5mAh cm at current density of-2SEM topography of the deposition product on the working electrode after the deposition capacity of (1).
FIG. 8 shows the discharge of 0.5mAh cm of the calcium metal half-cell in example 1-2An elemental analysis chart of a deposit on a working electrode, wherein (a) is Ca metal and (b) is Na metal.
FIG. 9 is an SEM topography of the residue on the working electrode when the calcium metal half cell of example 1 was charged to 1V (stripped state).
FIG. 10 is a diagram showing the elemental analysis of the residue on the working electrode when the calcium metal half-cell in example 1 was charged to 1V (peeled state), wherein (a) is Ca metal and (b) is Na metal.
FIG. 11 shows the calcium metal half cell of example 1 at 1mA cm-2Current density of 1mAh cm-2X-ray diffraction analysis of the deposition product on the working electrode after the deposition capacity of (2).
FIG. 12 shows the calcium metal half cell of example 1 at 1mA cm-2Current density of 1mAh cm-2Cross-sectional SEM morphology and elemental analysis plots of the deposition product on the working electrode after the deposition capacity of (1).
FIG. 13 shows the calcium metal half-cell at 1mA cm for comparative example 2 and example 2-2Deposition of 0.5mAh cm at current density of-2Long cycle performance comparison of deposition capacity of (a).
FIG. 14 shows the calcium metal half cell of example 3 at 1mA cm-2Deposition of 0.5mAh cm at current density of-2Long cycle performance of the deposition capacity of (a).
FIG. 15 shows the calcium metal half cell of example 3 at 1mA cm-2Current density of 1mAh cm-2Cross-sectional SEM morphology and elemental analysis plots of the product deposited on the working electrode after deposition of the capacity.
FIG. 16 shows the calcium metal half-cell concentration at 1mA cm for comparative example 3 (with gold as the working electrode) and example 1 (with carbon-coated aluminum foil as the working electrode)-2Deposition of 0.5mAh cm at current density of-2Long cycle performance comparison of deposition capacity of (a).
FIG. 17 shows comparative example 4 (using aluminum foil as a working electrode) and example 1 (using aluminum foil as a working electrode)Carbon-coated aluminum foil as working electrode) at 1mA cm-2Deposition of 0.5mAh cm at current density of-2Long cycle performance comparison of deposition capacity of (a).
FIG. 18 shows a calcium metal half-cell of example 5 with a carbon nanotube film as the working electrode at 1mA cm-2Deposition of 0.5mAh cm at current density of-2Long cycle performance comparison of deposition capacity of (a).
FIG. 19 shows the calcium metal half cell of example 6 at 1mA cm-2Deposition of 0.5mAh cm at current density of-2Long cycle performance of the deposition capacity of (a).
Detailed Description
The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.
Comparative example 1
The present comparative example provides a calcium metal half-cell without electrolyte additive, the assembly method of which is:
mixing Ca (BH)4)2The THF is dissolved in THF at the concentration of 1.5mol/L to be used as electrolyte, a glass fiber membrane is used as a diaphragm, a carbon-coated aluminum foil is used as a working electrode, and a metallic calcium sheet is used as a counter electrode, so that a half cell is assembled.
Example 1
The assembly method of the calcium metal half-cell in the embodiment comprises the following steps:
mixing Ca (BH)4)2THF was dissolved in THF, and sodium borohydride (NaBH) was added thereto at the same time4) Dissolving to obtain electrolyte (wherein Ca (BH)4)2The THF concentration was 1.5mol L-1，NaBH4The concentration is 0.2mol L-1) The half-cell is assembled by taking the glass fiber membrane as a diaphragm, the carbon-coated aluminum foil as a working electrode and the metallic calcium sheet as a counter electrode.
FIG. 1 shows the calcium metal half-cell at 1mA cm for comparative example 1 and example 1-2Deposition of 0.5mAh cm at current density of-2Long cycle performance comparison of deposition capacity of (a). The results show that: calcium metal semielectrode in comparative example 1The coulombic efficiency of the first circle of the pool is 85 percent, the efficiency of the 2 nd circle is attenuated to 75 percent, and then the efficiency is gradually attenuated to 67 percent from the 15 th circle and only 23 percent from the 30 th circle. The first coulomb efficiency of the calcium metal half-cell in example 1 is-93%, then gradually increases and becomes stable, the coulomb efficiency reaches-99.6% in the 10 th cycle, can still keep-99.0% after 1000 cycles, and the average coulomb efficiency in the previous 1000 cycles reaches 99.2%.
FIG. 2 shows the calcium metal half-cell at 1mA cm for comparative example 1 and example 1-2Deposition of 0.5mAh cm at current density of-2First turn deposition lift off curve of deposition capacity. The results show that: the nucleation overpotential in comparative example 1 was 550mV, the growth overpotential was 250 mV; the nucleation overpotential and the growth overpotential in example 1 were only 160mV and 130mV, respectively.
Fig. 3 is a cyclic voltammogram of the calcium metal half-cells of comparative example 1 and example 1. The results show that example 1 has a much higher peak current than comparative example 1.
Fig. 4 is a tafel plot for the calcium metal half-cells of comparative example 1 and example 1. The results showed that the exchange current densities at the deposition and stripping stages in comparative example 1 were 0.065 and 0.004mA cm, respectively-2Whereas the exchange current densities of the deposition and stripping stages in example 1 were 0.748mA cm-211 times and 187 times, respectively, as in comparative example 1.
Fig. 5 is an electrochemical impedance spectrum of the calcium metal half-cell of comparative example 1 and example 1. The results show that the impedance in comparative example 1 is much larger than that in example 1.
FIGS. 6 and 7 are graphs showing the results of the calcium metal half-cell at 1mA cm for comparative example 1 and example 1, respectively-2Deposition of 0.5mAh cm at current density of-2After the deposition capacity, the deposition morphology of calcium metal on the working electrode. The results show that: the calcium metal in comparative example 1 was deposited in a loose film form, and the upper layer of the film was very likely to grow into the separator in the form of dendrites, thereby easily forming inactive calcium metal out of contact with the substrate, resulting in low coulombic efficiency. The calcium metal in the embodiment 1 is closely packed in a larger spherical shape, is closely contacted with the substrate and does not grow into the diaphragm, so that the loss of inactive calcium is greatly reduced, and the loss of inactive calcium is also reducedThe contact area of the calcium metal and the electrolyte is shown.
FIG. 8 shows the discharge of 0.5mAh cm of the calcium metal half-cell in example 1-2Elemental analysis of the product deposited on the working electrode, wherein (a) is Ca metal and (b) is Na metal. The results show that: the spherical deposition product contains calcium element and sodium element, which indicates that the deposition product may be calcium metal and sodium metal.
FIGS. 9 and 10 are the morphological and elemental analysis (where (a) is Ca metal and (b) is Na metal) on the working electrode when the calcium metal half-cell of example 1 was charged to 1V. The results show that: the spherical product deposited on the current collector is completely stripped, and almost no calcium element and sodium element exist. This indicates that the spherical products are reversible calcium metal and sodium metal.
FIG. 11 shows the calcium metal half cell of example 1 at 1mA cm-2Current density of 1mAh cm-2X-ray diffraction analysis of the deposition product on the working electrode after the deposition capacity of (2). The results show that: the deposition products are calcium metal and sodium metal.
FIG. 12 shows the calcium metal half cell of example 1 at 1mA cm-2Current density of 1mAh cm-2After the deposition capacity, the cross-sectional morphology and elemental analysis of the deposition product on the working electrode are shown. The results show that: the deposition products are metallic calcium and metallic sodium, the metallic sodium is at the lower layer, and the metallic calcium is at the upper layer. Indicating that the sodium metal substrate has a positive effect on the deposition of calcium metal.
Comparative example 2
The present comparative example provides a calcium metal half-cell without electrolyte additive, the assembly method of which is:
mixing Ca (BH)4)2The THF is dissolved in THF at the concentration of 1.0mol/L to be used as electrolyte, a glass fiber membrane is used as a diaphragm, a carbon-coated aluminum foil is used as a working electrode, and a metallic calcium sheet is used as a counter electrode, so that a half cell is assembled.
Example 2
The assembly method of the calcium metal half-cell in the embodiment comprises the following steps:
mixing Ca (BH)4)2THF was dissolved in THF, and sodium borohydride (NaBH) was added thereto at the same time4) After dissolution, obtain electricityHydrolysate (wherein Ca (BH)4)2The THF concentration was 1.0mol L-1，NaBH4The concentration is 0.2mol L-1) The half-cell is assembled by taking the glass fiber membrane as a diaphragm, the carbon-coated aluminum foil as a working electrode and the metallic calcium sheet as a counter electrode.
FIG. 13 shows the calcium metal half-cell at 1mAcm for comparative example 2 and example 2-2Deposition of 0.5mAh cm at current density of-2Long cycle performance comparison of deposition capacity of (a). The results show that: the calcium metal half-cell in comparative example 2 had a first cycle coulombic efficiency of 69.4% and then decayed rapidly, with a coulombic efficiency of only 16.7% after 25 cycles. The first-cycle coulombic efficiency of the calcium metal half-cell in example 2 is 94.3%, and the average coulombic efficiency of 600 cycles is as high as 99.1%.
Example 3
The assembly method of the calcium metal half-cell in the embodiment comprises the following steps:
mixing Ca (BH)4)2THF was dissolved in THF, and sodium borohydride (NaBH) was added thereto at the same time4) Dissolving to obtain electrolyte (wherein Ca (BH)4)2The THF concentration was 1.5mol L-1，NaBH4The concentration is 0.05mol L-1) The half-cell is assembled by taking the glass fiber membrane as a diaphragm, the carbon-coated aluminum foil as a working electrode and the metallic calcium sheet as a counter electrode.
FIG. 14 shows the results of the calcium metal half-cell of this example at 1mA cm-2Deposition of 0.5mAh cm at current density of-2Long cycle performance of the deposition capacity of (a). The result shows that the first circulation coulombic efficiency of the half-cell is 97.0%, and the average coulombic efficiency of 500 circulations is as high as 99.0%.
FIG. 15 shows the results of the calcium metal half-cell of this example at 1mA cm-2Current density of 1mAh cm-2After depositing the volume, cross-sectional SEM morphology and elemental analysis of the product deposited on the working electrode. The results show that: when the amount of sodium borohydride additive is reduced, the amount of metallic sodium in the deposition product is significantly reduced, and although it has some effect on cycle life, it is still at an international advanced level.
Comparative example 3
The assembly method of the calcium metal half-cell in the embodiment comprises the following steps:
mixing Ca (BH)4)2THF was dissolved in THF, and sodium borohydride (NaBH) was added thereto at the same time4) Dissolving to obtain electrolyte (wherein Ca (BH)4)2The THF concentration was 1.5mol L-1，NaBH4The concentration is 0.2mol L-1) The glass fiber membrane is used as a diaphragm, the noble metal gold is used as a working electrode, and the metal calcium sheet is used as a counter electrode to assemble the half-cell.
FIG. 16 shows the calcium metal half-cell concentration at 1mA cm for comparative example 3 (with gold as the working electrode) and example 1 (with carbon-coated aluminum foil as the working electrode)-2Deposition of 0.5mAh cm at current density of-2Long cycle performance comparison of deposition capacity of (a). The results show that: the coulombic efficiency of the first circle of the half-cell assembled by taking gold as a current collector is 96%, and the average coulombic efficiency of 300 circles of circulation is 99.4%. In example 1, the coulombic efficiency of the first turn of the half-cell assembled by using the carbon-coated aluminum foil as the current collector is 93%, the average efficiency of 1000 cycles is 99.2%, and the half-cell assembled by using the carbon-coated aluminum foil as the current collector has the same high coulombic efficiency and long cycle life as the half-cell assembled by using the noble metal gold as the current collector.
Comparative example 4
The assembly method of the calcium metal half-cell in the embodiment comprises the following steps:
mixing Ca (BH)4)2THF was dissolved in THF, and sodium borohydride (NaBH) was added thereto at the same time4) Dissolving to obtain electrolyte (wherein Ca (BH)4)2The THF concentration was 1.5mol L-1，NaBH4The concentration is 0.2mol L-1) The half-cell is assembled by taking the glass fiber membrane as a diaphragm, the aluminum foil as a working electrode and the metal calcium sheet as a counter electrode.
FIG. 17 shows the results of comparison example 4 (using aluminum foil as a working electrode) and example 1 (using carbon-coated aluminum foil as a working electrode) at 1mA cm-2Deposition of 0.5mAh cm at current density of-2Long cycle performance comparison of deposition capacity of (a). The results show that: the initial coulombic efficiency of the half-cell assembled by using the aluminum foil as the current collector is only about 50 percent, the half-cell is very easy to overcharge after being cycled for a plurality of times to cause short circuit failure, and the average coulombic efficiency and the cycle life are far inferior to those of the half-cell assembled by using the carbon-coated aluminum foil as the current collectorAnd (4) assembling the half cell. This indicates that the carbon material substrate has an important promoting effect on the electrodeposition of metallic calcium.
Example 5
The assembly method of the calcium metal half-cell in the embodiment comprises the following steps:
mixing Ca (BH)4)2THF was dissolved in THF, and sodium borohydride (NaBH) was added thereto at the same time4) Dissolving to obtain electrolyte (wherein Ca (BH)4)2The THF concentration was 1.5mol L-1，NaBH4The concentration is 0.2mol L-1) The half-cell is assembled by taking the glass fiber membrane as a diaphragm, the carbon nanotube membrane as a working electrode and the calcium metal sheet as a counter electrode.
FIG. 18 shows the working electrode of the calcium metal half-cell of this example, which is a carbon nanotube film at 1mA cm-2Deposition of 0.5mAh cm at current density of-2Long cycle performance comparison of deposition capacity of (a). The results show that: although the coulomb efficiency of the first circle of the half-cell assembled by taking the carbon nanotube film as the current collector is only 89%, the coulomb efficiency of the second circle is greatly improved, the average coulomb efficiency of 200 circles of circulation is also up to 98.8%, and the half-cell is still in the international advanced level at present. This further demonstrates that the carbon material substrate positively promotes the electrodeposition of metallic calcium.
Example 6
The assembly method of the calcium metal half-cell in the embodiment comprises the following steps:
half cells assembled in example 1 were used at 1mA cm-2Deposition of 0.5mAh cm at current density of-2After which the cell was disassembled, the working electrode was taken out and washed, and then the half-cell was assembled according to the half-cell assembly method in comparative example 1.
FIG. 19 shows the calcium metal half cell at 1mA cm in this example-2Deposition of 0.5mAh cm at current density of-2Long cycle performance of the deposition capacity of (a). The results show that: after a small amount of sodium metal is loaded on a current collector by an electrodeposition method, the stable long circulation of the calcium metal half-cell with higher coulombic efficiency can be realized even if electrolyte containing no additive is used, and the average coulombic efficiency of 400 cycles of circulation is 98.7%. This illustrates the introduction of elemental sodium to calciumThe electrolyte of the metal battery has a positive effect on the electrodeposition of metal calcium.
The embodiments of the present invention have been described in detail, but the embodiments are merely examples, and the present invention is not limited to the embodiments described above. Any equivalent modifications and substitutions to those skilled in the art are also within the scope of the present invention. Accordingly, equivalent changes and modifications made without departing from the spirit and scope of the present invention should be covered by the present invention.

Claims (10)

1. A method for improving the performance of a calcium metal battery is characterized by comprising the following steps: at least one of sodium borohydride and potassium borohydride is added into the electrolyte as an additive, and/or at least one of sodium metal and potassium metal is loaded on the negative current collector, and/or at least one of sodium borohydride and potassium borohydride is loaded on the diaphragm.
2. A calcium metal battery electrolyte is characterized in that: comprises a solvent, a calcium salt and an additive, wherein the additive is at least one of sodium borohydride and potassium borohydride.
3. The calcium metal battery electrolyte of claim 2, wherein: the solvent is at least one of tetrahydrofuran, dimethyl tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, 1, 3-dioxolane, dimethyl sulfoxide, ethylenediamine, N-dimethylformamide and pyridine.
4. The calcium metal battery electrolyte of claim 2, wherein: the calcium salt is one or more of calcium bis (tetrahydrofuran) borohydride, calcium tetrafluoroborate, calcium hexafluorophosphate and calcium trifluoromethanesulfonate.
5. The calcium metal battery electrolyte of claim 2, wherein: in the electrolyte, the concentration of the calcium salt is 0.5mol/L-2.0 mol/L.
6. The calcium metal battery electrolyte of claim 2, wherein: in the electrolyte, the concentration of the additive is 0.01mol/L-0.5 mol/L.
7. The utility model provides a calcium metal battery, includes calcium metal negative pole, negative current collector, electrolyte, positive pole and diaphragm, its characterized in that: the electrolyte is the electrolyte according to any one of claims 2 to 6.
8. The calcium metal battery of claim 7, wherein: the negative current collector adopts one of a carbon-coated aluminum foil, a carbon-coated copper foil and other carbon material substrates.
9. The calcium metal battery of claim 7 or 8, wherein: at least one of sodium metal and potassium metal is loaded on the negative current collector.
10. The calcium metal battery of claim 7 or 8, wherein: at least one of sodium borohydride and potassium borohydride is loaded on the diaphragm.
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